WO2015114239A1 - Method for producing a covering element made from fibres impregnated with bitumen having improved fire properties, and composition - Google Patents
Method for producing a covering element made from fibres impregnated with bitumen having improved fire properties, and composition Download PDFInfo
- Publication number
- WO2015114239A1 WO2015114239A1 PCT/FR2015/050159 FR2015050159W WO2015114239A1 WO 2015114239 A1 WO2015114239 A1 WO 2015114239A1 FR 2015050159 W FR2015050159 W FR 2015050159W WO 2015114239 A1 WO2015114239 A1 WO 2015114239A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- liquid composition
- coating
- fire
- additive
- bitumen
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 96
- 239000010426 asphalt Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 68
- 239000011248 coating agent Substances 0.000 claims abstract description 62
- 238000000576 coating method Methods 0.000 claims abstract description 62
- 239000000654 additive Substances 0.000 claims abstract description 53
- 230000000996 additive effect Effects 0.000 claims abstract description 53
- 239000000835 fiber Substances 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000010439 graphite Substances 0.000 claims abstract description 34
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000049 pigment Substances 0.000 claims abstract description 20
- 239000002826 coolant Substances 0.000 claims abstract description 19
- 229920003043 Cellulose fiber Polymers 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 15
- 229910021540 colemanite Inorganic materials 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 11
- 238000004040 coloring Methods 0.000 claims description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229920002396 Polyurea Polymers 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920006241 epoxy vinyl ester resin Polymers 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920005749 polyurethane resin Polymers 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 230000011218 segmentation Effects 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- 238000003287 bathing Methods 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 abstract description 4
- 239000001913 cellulose Substances 0.000 abstract description 4
- 230000009970 fire resistant effect Effects 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D3/00—Roof covering by making use of flat or curved slabs or stiff sheets
- E04D3/24—Roof covering by making use of flat or curved slabs or stiff sheets with special cross-section, e.g. with corrugations on both sides, with ribs, flanges, or the like
- E04D3/32—Roof covering by making use of flat or curved slabs or stiff sheets with special cross-section, e.g. with corrugations on both sides, with ribs, flanges, or the like of plastics, fibrous materials, or asbestos cement
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C09D161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N5/00—Roofing materials comprising a fibrous web coated with bitumen or another polymer, e.g. pitch
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N5/00—Roofing materials comprising a fibrous web coated with bitumen or another polymer, e.g. pitch
- D06N5/003—Roofing materials comprising a fibrous web coated with bitumen or another polymer, e.g. pitch coated with bitumen
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D3/00—Roof covering by making use of flat or curved slabs or stiff sheets
- E04D3/24—Roof covering by making use of flat or curved slabs or stiff sheets with special cross-section, e.g. with corrugations on both sides, with ribs, flanges, or the like
- E04D3/34—Roof covering by making use of flat or curved slabs or stiff sheets with special cross-section, e.g. with corrugations on both sides, with ribs, flanges, or the like of specified materials, or of combinations of materials, not covered by any one of groups E04D3/26 - E04D3/32
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
- E04D5/02—Roof covering by making use of flexible material, e.g. supplied in roll form of materials impregnated with sealing substances, e.g. roofing felt
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2201/00—Chemical constitution of the fibres, threads or yarns
- D06N2201/04—Vegetal fibres
- D06N2201/042—Cellulose fibres, e.g. cotton
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/08—Properties of the materials having optical properties
- D06N2209/0807—Coloured
- D06N2209/0823—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
Definitions
- the present invention relates to a method of producing a roofing element made of fibers, in particular cellulose, impregnated with bitumen which has an improved fire behavior, a device for carrying out the process and a composition that can be used at this end. It has applications in the field of the manufacture of building elements and in particular covering elements, in particular corrugated sheets or other covering elements including those covering lines or singular points of the roofs.
- roofing elements made of cellulose fibers impregnated with bitumen have been used for many years.
- graphite in their composition.
- dry spreading dusting of graphite particles on one of the two opposite faces of the cover elements with means allowing said particles to remain attached to said surface.
- the equipment necessary to perform such an operation are complex and delicate adjustment since the particles are widespread, either on elements to be shaped, or on already shaped elements, including corrugated plates, making it difficult to spread homogeneously on the whole surface.
- they are specific equipment, dedicated to the spreading of graphite particles and which can be difficult to install within an already existing production line.
- Document FR2372927 describes a process for producing hardly combustible corrugated bituminous plates in which an aqueous composition of specific formulation but not mentioning graphite is cast or sprayed.
- EP2617894 discloses a fire-resistant bituminous cellulosic blanket and a method of manufacture in which graphite is deposited dry on a mattress covered with a bonding primer layer.
- the document EP2634306 describes a protective membrane and its manufacturing process in which the membrane is first soaked in bitumen and then receives particles.
- the subject of the invention is thus a process for producing a bitumen-impregnated fiber roofing element comprising a step of coating at least one of two faces of a fiber mat, said fibers being at least for one part of them natural fibers, said natural fibers being in particular cellulose fibers, followed by a step of impregnation with bitumen, the coating being carried out by a liquid composition comprising at least one resin and / or at least one a pigment.
- an additive having fireproof properties and comprising at least graphite and a cooling agent there is added to the liquid composition an additive having fireproof properties and comprising at least graphite and a cooling agent.
- the following means can be used alone. or in any technically possible combination, are used:
- the liquid composition is a coloring composition comprising at least one pigment and at least one resin and an additive with fire-resistant properties and comprising at least graphite and a cooling agent is added to the liquid composition,
- the step of coating the fiber mat is carried out before the impregnation with the bitumen
- the fibers are all natural fibers
- the natural fibers comprise cellulose fibers
- the natural fibers are practically all cellulose fibers
- the fibers are cellulose fibers
- cellulose comes from recycled paper and / or cardboard
- the liquid composition comprises at least one resin
- the liquid composition comprises at least one pigment in order to form a coloring composition
- the liquid composition further comprises at least one resin for the resin in order to form a coloring composition
- the liquid composition is a coloring composition comprising at least one pigment and at least one resin,
- the fiber mattress is a flat / flat mattress
- the cooling agent is colemanite
- the fire-resistant additive only contains graphite and colemanite
- an anti-fire additive is used in which the cooling agent is colemanite,
- the at least one resin is chosen from: epoxy resins, polyurethane resins, polyurea resins, polyurea-formaldehyde resins, melamine-formaldehyde resins, epoxy vinyl ester resins or vinylester resins,
- the at least one pigment is chosen from: metal oxides such as iron oxide and chromium oxide
- a liquid composition comprising the fire-resistant additive which comprises at least one resin chosen from: epoxy resins, polyurethane resins, polyurea resins, polyurea-formaldehyde resins, melamine-formaldehyde resins, resins, is used.
- coating is carried out according to determined procedural modalities and with predetermined proportions of the compounds of the liquid composition in order to obtain a covering element having specific weights of said compounds,
- the amount of resin represents from 0.5 to 3% by weight of the cover element
- the amount of pigment represents from 0.5 to 3% by weight of the cover element
- the amount of cooling agent represents from 1 to 7% by weight of the cover element
- the amount of cooling agent is preferably from 2 to 5% by weight of the cover element
- the amount of graphite represents from 1 to 7% by weight of the cover element
- the amount of graphite preferably represents from 2 to 5% by weight of the cover element
- the amount of resin represents from 0.5 to 3% by weight of the covering element
- the amount of pigment represents from 0.5 to 3% by weight of the covering element
- the amount of cooling agent represents from 1 to 7% by weight of the cover element
- the amount of graphite represents from 1 to 7% by weight of the cover element
- the graphite is in flakes or flakes
- the flake or flake graphite has a size range chosen between 70 Mesh and 220 Mesh, ie between 210 mm and 62 mm,
- the coating of the mattress with the liquid composition comprising the fire-resistant additive is carried out with a roller
- the coating of the mattress is a roll coating of the liquid composition comprising the fire-resistant additive
- the coating of the mattress is a coating with a knife or scraper of the liquid composition comprising the fire-resistant additive
- the coating of the mattress is a spray coating of the liquid composition comprising the fire-resistant additive
- the liquid composition comprising the fire-resistant additive intended to be coated on the mattress is kept under constant stirring by an agitator, the constant stirring of the liquid composition comprising the fire-retardant additive concerns the composition stored in a coating tank in which the coating roll is immersed / tempered,
- the constant stirring of the liquid composition comprising the fire-resistant additive concerns the composition stored in a system for storing and / or preparing said composition distinct from the coating tank,
- the stirrer is a vibratory stirrer disposed on the wall of the coating tank, in particular with sound or ultrasonic vibrations,
- the agitator is a mechanical stirrer disposed within the liquid composition, the stirrer is chosen from Archimedean screw stirrers, with a helical ribbon, or any other equivalent type of stirrer,
- the method further comprises a step of drying and setting the liquid composition comprising the fire-resistant additive which has been coated on the mattress,
- the fiber mat is discontinuous and corresponds to fiber plates
- the fiber mat is continuous, said mat being cut into plates in a segmentation step subsequent to the coating step and prior to the bitumen impregnation step, the impregnation with the bitumen being effected on individual plates,
- the method further comprises a step of shaping the mattress after the coating step and prior to the bitumen impregnation step;
- the conformation step is a step of producing corrugations in a roller undulator
- At least one coating roll and a coating tank are used for the liquid composition comprising the fire-resistant additive, said at least one coating roll bathed within the coating tank in said liquid composition. comprising the anti-fire additive and said coating tank comprises said stirrer for maintaining under constant agitation said composition comprising the fire-resistant additive.
- the invention also relates to a device for coating a fiber mat, said fibers being at least for part of them natural fibers, said natural fibers being in particular cellulose fibers, and which is especially intended to be put implemented in the process and which comprises at least one coating roll and a coating tank for a liquid composition comprising a fire-resistant additive, said at least one coating roll bathed within the coating tank in said liquid composition comprising the fire-resistant additive and said coating tank comprises an agitator for maintaining under constant agitation said liquid composition comprising the fire-resistant additive.
- the agitator is screw Archimedes and / or the agitator and said at least one coating roll have parallel axes of rotation.
- the liquid composition is a coloring composition.
- the invention also relates to a liquid composition comprising an anti-fire additive for use in the process presented and as it comprises, for the liquid composition part, at least one resin and, optionally, one or more pigments, and for the fire retardant additive part, graphite and a coolant.
- the coolant is colemanite.
- the invention also relates, in itself, to a step of coating a fiber mat, said fibers being at least for part of them natural fibers, said natural fibers being in particular cellulose fibers, for example a liquid composition comprising an anti-fire additive according to the invention described.
- a drying / setting step of the liquid composition comprising the fire-resistant additive which has been coated on the mattress.
- the production of the cover elements is simplified because in a single operation the coloring with the coloring composition comprising at least one pigment and at least one resin and the protection against fire is obtained since the composition also comprises graphite. and a coolant, all wet by roll coating.
- the implementation of rollers allows a controlled application with a certain pressure of the composition, which leads to a better grip / incorporation of the elements of the composition in the fiber mat, in particular flakes or flakes of graphite.
- the roll coating also makes it possible to envisage making particular colored patterns on the mattress.
- Figure 1 which shows a device for coating a mat of natural fibers which are here cellulose fibers.
- the coating device 1 of FIG. 1 is specially configured for the implementation of the method of the invention since it allows a homogeneous coating of a liquid composition comprising an anti-fire additive by means of a coating roll 2 which quenching / bath partially in said composition 5.
- the liquid composition 5 comprising the fire-resistant additive is contained in a coating tank 6 of the device 1 and is kept under constant stirring by an agitator 7 so that said composition remains substantially homogeneous .
- the axes of rotation of the coating roll 2 and the stirrer 7 are parallel to each other.
- a counter-roller 3 presses the mattress 4 of cellulose fibers against the coating roll 2. Counter pressure adjusting and regulating means are implemented.
- the cellulose fibers are in the form of a continuous cellulose fiber mat continuously passing between the coating roller 2 and the counter roller 3.
- the liquid composition comprising the fire-resistant additive preferably comes from a system for storing and / or preparing upstream of said composition, not shown, and the device comprises means for transferring and regulating the level of the liquid composition 5 in the coating tank 6.
- the means for adjusting the amount of liquid composition comprising the fire-resistant additive which is deposited on the cellulose fiber mat and which is therefore found in the finished product it is possible to mention the adjustment of the level of the liquid composition. 5 in the coating tank 6 causing the coating roll 2 to quench more or less in the liquid composition.
- This upstream system comprises means for preparing the liquid composition comprising the fire-resistant additive with a mixer allowing mixtures at different speeds.
- a low pressure displacement pump is implemented between the storage system and / or preparation and the coating tank 6.
- a liquid composition of the dye composition type comprising the fire retardant is prepared by first mixing pigment in water in a high speed mixing mixer. Surfactants are preferably added to facilitate mixing between the water and the pigment (s). Then, the colemanite is still added to the mixer at high mixing speed, preferably by gradual addition of the colemanite. Once this mixture has been achieved, the graphite is gradually added and this time is mixed at a lower speed. Then, one or more compatible resins are added which are mixed at this lower speed or at an even lower speed. During these phases, viscosity and / or other parameters are adjusted if necessary.
- Colemanite is a coolant, that is, it is a substance that avoids too high a rise in heat of the fiber mat when it is heated. Indeed, in itself, graphite is heat conductor. However, during the drying operation of the fiber mat after coating, the mattress is heated to remove water / moisture remaining in the mattress. Indeed, the viscous solution containing among others graphite, is applied on the mattress while it still contains a certain humidity. This heating for drying, which also allows the setting / drying of the liquid coating composition, will therefore also heat the graphite and the temperature of the graphite in contact with the fiber mat may cause overheating of these fibers and therefore a risk of damage to fibers.
- the cooling agent therefore has the role of controlling the temperature at the level of the fiber mat with the release of water molecules in the case of the species of colemanite.
- a cooling agent in the context of the invention, may correspond to a substance which, by a physicochemical reaction, causes a lowering of temperature, vaporization of water in the case of colemanite, and or by a physical effect limits the heat transfer by barrier and / or reflection.
- the liquid composition comprising the fire-resistant additive which is coated on the mattress is preferably in liquid form with a specific fluidity to allow a part of said liquid composition comprising the fire-resistant additive to be able to diffuse at least in part inside the thickness of the cellulose fiber mat.
- the liquid composition comprising the fire-resistant additive impregnates, at least in part, the thickness of the mattress in addition to covering on the surface at least one of the two faces of the cellulose fiber mat.
- the liquid composition comprising the fire-resistant additive may be of a more pasty consistency with application to the knife or scraper on the cellulose fiber mat.
- the graphite employed has a range of sizes and shapes of determined particles and, preferably, it uses graphite in the form of flakes or flakes which remain essentially on the surface of the cellulose fiber mat and which diffuse little in its thickness. .
- the graphite is chosen, in particular in shape / structure and / or size, as well as the operational parameters of the process for producing the covering elements, so that it remains in suspension in the liquid composition until it is applied. and that it remains inert during post-coating drying and bitumen impregnation. It is indeed preferable that there is no expansion of the graphite before the end of the process of producing the covering elements.
- the process of the present invention can allow more or less diffusion of the graphite into the thickness of the cellulose fiber mat if desired by changing the size and / or the shape of the graphite used.
- the mattress After coating the cellulose fiber mat with the liquid composition comprising the fire-resistant additive, the mattress is dried in a drying oven which allows both the setting / crosslinking of the liquid composition comprising the fire-resistant additive and removal of water / moisture that can still be contained in the mattress.
- the drying oven is at a temperature between 150 ° C and 400 ° C and preferably between 200 ° C and 300 ° C.
- the mat or the plates it is desirable for the mat or the plates to be substantially dry.
- the cellulose fiber mat is shaped during a conformation step of the mattress for, for example, producing corrugations, and is then passed through the drying oven.
- the cellulose fiber mat is cut into plates and it is these plates which are then impregnated with hot bitumen. Until the cutting of the mattress plate, the process is continuous, the cellulose fiber mat continuously scrolling for coating, shaping and drying in the drying oven.
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Abstract
The invention concerns a method for producing a covering element made from natural fibres, in particular cellulose, impregnated with bitumen, comprising a step of coating at least one of two faces of a fibre mat (4) followed by a step of impregnating with bitumen, the coating being carried out with a liquid composition (5) comprising at least one resin and/or at least one pigment. The liquid composition is a dye composition comprising at least one pigment and at least one resin, and the method involves adding an additive to the liquid composition (5), said additive having fireproof properties and comprising at least graphite and a cooling agent. Preferably, the mat (4) is coated with the liquid composition comprising the fireproof additive using a roller.
Description
PROCEDE DE REALISATION D'UN ELEMENT DE COUVERTURE EN METHOD OF MAKING A COVERING ELEMENT IN
FIBRES IMPREGNE DE BITUME A COMPORTEMENT AU FEU AMELIORE ET COMPOSITION IMPREGNATED BITUMEN FIBERS WITH IMPROVED FIRE BEHAVIOR AND COMPOSITION
La présente invention concerne un procédé de réalisation d'un élément de couverture de toiture en fibres, notamment de cellulose, imprégné de bitume qui a un comportement au feu amélioré, un dispositif pour la mise en œuvre du procédé ainsi qu'une composition utilisable à cette fin. Elle a des applications dans le domaine de la fabrication des éléments de construction et notamment des éléments de couverture, notamment plaques ondulées ou autres éléments de couverture dont ceux couvrant des lignes ou points singuliers des toitures. The present invention relates to a method of producing a roofing element made of fibers, in particular cellulose, impregnated with bitumen which has an improved fire behavior, a device for carrying out the process and a composition that can be used at this end. It has applications in the field of the manufacture of building elements and in particular covering elements, in particular corrugated sheets or other covering elements including those covering lines or singular points of the roofs.
Les éléments de couverture en fibres de cellulose imprégnés de bitume sont utilisés depuis de nombreuses années. Afin d'améliorer leur comportement au feu, il a été proposé d'utiliser du graphite dans leur composition. En particulier, il a été proposé le répandage à sec : saupoudrage de particules de graphite sur une des deux faces opposées des éléments de couverture avec un moyen permettant aux dites particules de rester solidaires de ladite surface. Roofing elements made of cellulose fibers impregnated with bitumen have been used for many years. In order to improve their fire behavior, it has been proposed to use graphite in their composition. In particular, it has been proposed dry spreading: dusting of graphite particles on one of the two opposite faces of the cover elements with means allowing said particles to remain attached to said surface.
Les équipements nécessaires pour réaliser une telle opération sont complexes et d'un réglage délicat étant donné que les particules sont répandues, soit sur des éléments amenés à être conformés, soit sur des éléments déjà conformés, notamment des plaques ondulées, rendant difficile un répandage homogène sur toute la surface. De plus, ce sont des équipements spécifiques, dédiés au répandage des particules de graphite et qui peuvent être difficiles à installer au sein d'une chaîne de fabrication déjà existante. The equipment necessary to perform such an operation are complex and delicate adjustment since the particles are widespread, either on elements to be shaped, or on already shaped elements, including corrugated plates, making it difficult to spread homogeneously on the whole surface. In addition, they are specific equipment, dedicated to the spreading of graphite particles and which can be difficult to install within an already existing production line.
On connaît le document FR2372927 qui décrit un procédé de fabrication de plaques ondulées bituminées difficilement combustibles dans lequel on coule ou pulvérise une composition aqueuse de formulation spécifique mais ne mentionnant pas le graphite. Le document EP2617894 décrit une plaque de couverture cellulosique bituminée résistant au feu et un procédé de fabrication dans lequel du graphite est déposé par voie sèche sur un matelas recouvert d'une couche de primaire de collage. Le document EP2634306 décrit une membrane de protection et son procédé de fabrication dans lequel la membrane est d'abord trempée dans du bitume puis reçoit des particules. Document FR2372927 describes a process for producing hardly combustible corrugated bituminous plates in which an aqueous composition of specific formulation but not mentioning graphite is cast or sprayed. EP2617894 discloses a fire-resistant bituminous cellulosic blanket and a method of manufacture in which graphite is deposited dry on a mattress covered with a bonding primer layer. The document EP2634306 describes a protective membrane and its manufacturing process in which the membrane is first soaked in bitumen and then receives particles.
Il est ici proposé un procédé de répandage de graphite incorporé dans une composition liquide et un dispositif correspondant qui peuvent être facilement combinés à un procédé et un équipement existants d'une chaîne de fabrication d'éléments de couverture en fibres notamment de cellulose imprégnés de bitume. Il est plus spécifiquement proposé de les utiliser au sein d'un équipement destiné à la coloration de l'élément de couverture, soit au sein d'un équipement déjà existant, soit lors de l'installation d'une nouvelle chaîne de fabrication d'éléments de couverture.
L'invention a ainsi pour objet un procédé de réalisation d'un élément de couverture en fibres imprégné de bitume comportant une étape d'enduction d'au moins une de deux faces d'un matelas de fibres, lesdites fibres étant au moins pour une partie d'entre elles des fibres naturelles, lesdites fibres naturelles étant notamment des fibres de cellulose, suivie d'une étape d'imprégnation par le bitume, l'enduction étant réalisée par une composition liquide comportant au moins une résine et/ou au moins un pigment. Here it is proposed a method of spreading graphite incorporated in a liquid composition and a corresponding device that can be easily combined with an existing process and equipment of a production line of fiber-reinforced fiber elements including cellulose impregnated with bitumen . It is more specifically proposed to use them in equipment intended for coloring the cover element, either within existing equipment or during the installation of a new production line. cover elements. The subject of the invention is thus a process for producing a bitumen-impregnated fiber roofing element comprising a step of coating at least one of two faces of a fiber mat, said fibers being at least for one part of them natural fibers, said natural fibers being in particular cellulose fibers, followed by a step of impregnation with bitumen, the coating being carried out by a liquid composition comprising at least one resin and / or at least one a pigment.
Selon l'invention, on ajoute à la composition liquide un additif ayant des propriétés anti-feu et comportant au moins du graphite et un agent de refroidissement, Dans divers modes de mise en œuvre de l'invention, les moyens suivants pouvant être utilisés seuls ou selon toutes les combinaisons techniquement possibles, sont employés : According to the invention, there is added to the liquid composition an additive having fireproof properties and comprising at least graphite and a cooling agent. In various embodiments of the invention, the following means can be used alone. or in any technically possible combination, are used:
- la composition liquide est une composition colorante comportant au moins un pigment et au moins une résine et on ajoute à la composition liquide un additif ayant des propriétés anti-feu et comportant au moins du graphite et un agent de refroidissement, the liquid composition is a coloring composition comprising at least one pigment and at least one resin and an additive with fire-resistant properties and comprising at least graphite and a cooling agent is added to the liquid composition,
- l'étape d'enduction du matelas de fibres s'effectue avant l'imprégnation par le bitume,the step of coating the fiber mat is carried out before the impregnation with the bitumen,
- les fibres sont toutes des fibres naturelles, the fibers are all natural fibers,
- les fibres naturelles comportent des fibres de cellulose, the natural fibers comprise cellulose fibers,
- les fibres naturelles sont pratiquement toutes des fibres de cellulose, the natural fibers are practically all cellulose fibers,
- les fibres sont des fibres de cellulose, the fibers are cellulose fibers,
- la cellulose provient de papiers et/ou cartons recyclés, cellulose comes from recycled paper and / or cardboard,
- la composition liquide comporte au moins une résine, the liquid composition comprises at least one resin,
- la composition liquide comporte au moins un pigment afin de former une composition colorante, the liquid composition comprises at least one pigment in order to form a coloring composition,
- la composition liquide comporte en outre de la résine au moins un pigment afin de former une composition colorante, the liquid composition further comprises at least one resin for the resin in order to form a coloring composition,
- de préférence, la composition liquide est une composition colorante comportant au moins un pigment et au moins une résine, preferably, the liquid composition is a coloring composition comprising at least one pigment and at least one resin,
- le matelas de fibres est un matelas plan/plat, the fiber mattress is a flat / flat mattress,
- l'agent de refroidissement est de la colémanite, the cooling agent is colemanite,
- l'additif anti-feu comporte seulement du graphite et de la colémanite, - the fire-resistant additive only contains graphite and colemanite,
- on met en œuvre un additif anti-feu dans lequel l'agent de refroidissement est de la colémanite, an anti-fire additive is used in which the cooling agent is colemanite,
- la au moins une résine est choisie parmi : les résines époxydes, les résines polyuréthanes, les résines polyurées, les résines polyurée-formaldéhydes, les résines mélamines-formaldéhydes, les résines époxyvinylesters ou les résines vinylesters, the at least one resin is chosen from: epoxy resins, polyurethane resins, polyurea resins, polyurea-formaldehyde resins, melamine-formaldehyde resins, epoxy vinyl ester resins or vinylester resins,
- le au moins un pigment est choisi parmi : les oxydes métalliques tels que l'oxyde de fer et l'oxyde de chrome,
- on met en œuvre une composition liquide comportant l'additif anti-feu qui comporte au moins une résine choisie parmi : les résines époxydes, les résines polyuréthanes, les résines polyurées, les résines polyurée-formaldéhydes, les résines mélamines- formaldéhydes, les résines époxyvinylesters ou les résines vinylesters, et la composition liquide, dans le cas où elle est une composition colorante, comportant l'additif anti-feu comporte au moins un pigment choisi parmi : les oxydes métalliques tels que l'oxyde de fer et l'oxyde de chrome, the at least one pigment is chosen from: metal oxides such as iron oxide and chromium oxide, a liquid composition comprising the fire-resistant additive which comprises at least one resin chosen from: epoxy resins, polyurethane resins, polyurea resins, polyurea-formaldehyde resins, melamine-formaldehyde resins, resins, is used. epoxyvinylesters or vinylester resins, and the liquid composition, in the case where it is a coloring composition, comprising the anti-fire additive comprises at least one pigment chosen from: metal oxides such as iron oxide and oxide of chrome,
- on procède à l'enduction selon des modalités procédurales déterminées et avec des proportions déterminées des composés de la composition liquide afin d'obtenir un élément de couverture ayant des poids déterminés desdits composés, coating is carried out according to determined procedural modalities and with predetermined proportions of the compounds of the liquid composition in order to obtain a covering element having specific weights of said compounds,
- la quantité de résine représente de 0,5 à 3 % en poids de l'élément de couverture, the amount of resin represents from 0.5 to 3% by weight of the cover element,
- la quantité de pigment représente de 0,5 à 3 % en poids de l'élément de couverture,the amount of pigment represents from 0.5 to 3% by weight of the cover element,
- la quantité d'agent de refroidissement représente de 1 à 7 % en poids de l'élément de couverture, the amount of cooling agent represents from 1 to 7% by weight of the cover element,
- la quantité d'agent de refroidissement représente de préférence de 2 à 5 % en poids de l'élément de couverture, the amount of cooling agent is preferably from 2 to 5% by weight of the cover element,
- la quantité de graphite représente de 1 à 7 % en poids de l'élément de couverture, the amount of graphite represents from 1 to 7% by weight of the cover element,
- la quantité de graphite représente de préférence de 2 à 5 % en poids de l'élément de couverture, the amount of graphite preferably represents from 2 to 5% by weight of the cover element,
- la quantité de résine représente de 0,5 à 3 % en poids de l'élément de couverture, la quantité de pigment représente de 0,5 à 3 % en poids de l'élément de couverture, la quantité d'agent de refroidissement représente de 1 à 7 % en poids de l'élément de couverture, et la quantité de graphite représente de 1 à 7 % en poids de l'élément de couverture, the amount of resin represents from 0.5 to 3% by weight of the covering element, the amount of pigment represents from 0.5 to 3% by weight of the covering element, the amount of cooling agent represents from 1 to 7% by weight of the cover element, and the amount of graphite represents from 1 to 7% by weight of the cover element,
- le graphite est en flocons ou paillettes, - the graphite is in flakes or flakes,
- le graphite en flocons ou paillettes a une gamme de taille choisie entre 70 Mesh et 220 Mesh, soit entre 210 mm et 62 mm, the flake or flake graphite has a size range chosen between 70 Mesh and 220 Mesh, ie between 210 mm and 62 mm,
- l'enduction du matelas avec la composition liquide comportant l'additif anti-feu est réalisée au rouleau, the coating of the mattress with the liquid composition comprising the fire-resistant additive is carried out with a roller,
- l'enduction du matelas est une enduction au rouleau de la composition liquide comportant l'additif anti-feu, the coating of the mattress is a roll coating of the liquid composition comprising the fire-resistant additive,
- l'enduction du matelas est une enduction au couteau ou racloir de la composition liquide comportant l'additif anti-feu, the coating of the mattress is a coating with a knife or scraper of the liquid composition comprising the fire-resistant additive,
- l'enduction du matelas est une enduction par pulvérisation de la composition liquide comportant l'additif anti-feu, the coating of the mattress is a spray coating of the liquid composition comprising the fire-resistant additive,
- la composition liquide comportant l'additif anti-feu destinée à être enduite sur le matelas est maintenue sous agitation constante par un agitateur,
- l'agitation constante de la composition liquide comportant l'additif anti-feu concerne la composition stockée dans un réservoir d'enduction dans lequel baigne/trempe le rouleau d'enduction, the liquid composition comprising the fire-resistant additive intended to be coated on the mattress is kept under constant stirring by an agitator, the constant stirring of the liquid composition comprising the fire-retardant additive concerns the composition stored in a coating tank in which the coating roll is immersed / tempered,
- l'agitation constante de la composition liquide comportant l'additif anti-feu concerne la composition stockée dans un système de stockage et/ou de préparation de ladite composition distinct du réservoir d'enduction, the constant stirring of the liquid composition comprising the fire-resistant additive concerns the composition stored in a system for storing and / or preparing said composition distinct from the coating tank,
- l'agitateur est un agitateur vibratoire disposé sur la paroi du réservoir d'enduction, notamment à vibrations sonores ou ultrasonores, the stirrer is a vibratory stirrer disposed on the wall of the coating tank, in particular with sound or ultrasonic vibrations,
- l'agitateur est un agitateur mécanique disposé au sein de la composition liquide, - l'agitateur est choisi parmi les agitateurs à vis d'Archimède, à ruban hélicoïdal, ou tout autre type équivalent d'agitateur, the agitator is a mechanical stirrer disposed within the liquid composition, the stirrer is chosen from Archimedean screw stirrers, with a helical ribbon, or any other equivalent type of stirrer,
- le procédé comporte en outre une étape de séchage et de prise de la composition liquide comportant l'additif anti-feu qui a été enduite sur le matelas, the method further comprises a step of drying and setting the liquid composition comprising the fire-resistant additive which has been coated on the mattress,
- le matelas de fibres est discontinu et correspond à des plaques de fibres, the fiber mat is discontinuous and corresponds to fiber plates,
- le matelas de fibres est continu, ledit matelas étant découpé en plaques dans une étape de segmentation postérieure à l'étape d'enduction et antérieure à l'étape d'imprégnation par le bitume, l'imprégnation par le bitume s'effectuant sur des plaques individuelles, - The fiber mat is continuous, said mat being cut into plates in a segmentation step subsequent to the coating step and prior to the bitumen impregnation step, the impregnation with the bitumen being effected on individual plates,
- le procédé comporte en outre une étape de conformation du matelas postérieurement à l'étape d'enduction et antérieurement à l'étape d'imprégnation par le bitume, the method further comprises a step of shaping the mattress after the coating step and prior to the bitumen impregnation step;
- l'étape de conformation est une étape de réalisation d'ondulations dans une ondulatrice à rouleaux, the conformation step is a step of producing corrugations in a roller undulator,
- on met en œuvre au moins un rouleau d'enduction et un réservoir d'enduction pour la composition liquide comportant l'additif anti-feu, ledit au moins un rouleau d'enduction baignant au sein du réservoir d'enduction dans ladite composition liquide comportant l'additif anti-feu et ledit réservoir d'enduction comporte ledit agitateur destiné à maintenir sous une agitation constante ladite composition comportant l'additif anti-feu. at least one coating roll and a coating tank are used for the liquid composition comprising the fire-resistant additive, said at least one coating roll bathed within the coating tank in said liquid composition. comprising the anti-fire additive and said coating tank comprises said stirrer for maintaining under constant agitation said composition comprising the fire-resistant additive.
L'invention concerne également un dispositif pour enduction d'un matelas de fibres, lesdites fibres étant au moins pour une partie d'entre elles des fibres naturelles, lesdites fibres naturelles étant notamment des fibres de cellulose, et qui est spécialement destiné à être mis en œuvre dans le procédé présenté et qui comporte au moins un rouleau d'enduction et un réservoir d'enduction pour une composition liquide comportant un additif anti-feu, ledit au moins un rouleau d'enduction baignant au sein du réservoir d'enduction dans ladite composition liquide comportant l'additif anti-feu et ledit réservoir d'enduction comporte un agitateur destiné à maintenir sous une agitation constante ladite composition liquide comportant l'additif anti-feu. Dans des modalités particulières, l'agitateur est à vis d'Archimède et/ou l'agitateur et ledit au moins un rouleau d'enduction ont des axes de rotation parallèles. De préférence, la composition liquide est une composition colorante.
L'invention concerne également une composition liquide comportant un additif anti-feu pour mise en œuvre dans le procédé présenté et telle qu'elle comporte, pour la partie de composition liquide, au moins une résine et, éventuellement, un ou des pigments, et pour la partie additif anti-feu, du graphite et un agent de refroidissement. En particulier, l'agent de refroidissement est de la colémanite. The invention also relates to a device for coating a fiber mat, said fibers being at least for part of them natural fibers, said natural fibers being in particular cellulose fibers, and which is especially intended to be put implemented in the process and which comprises at least one coating roll and a coating tank for a liquid composition comprising a fire-resistant additive, said at least one coating roll bathed within the coating tank in said liquid composition comprising the fire-resistant additive and said coating tank comprises an agitator for maintaining under constant agitation said liquid composition comprising the fire-resistant additive. In particular conditions, the agitator is screw Archimedes and / or the agitator and said at least one coating roll have parallel axes of rotation. Preferably, the liquid composition is a coloring composition. The invention also relates to a liquid composition comprising an anti-fire additive for use in the process presented and as it comprises, for the liquid composition part, at least one resin and, optionally, one or more pigments, and for the fire retardant additive part, graphite and a coolant. In particular, the coolant is colemanite.
L'invention concerne également, en elle-même, une étape d'enduction d'un matelas de fibres, lesdites fibres étant au moins pour une partie d'entre elles des fibres naturelles, lesdites fibres naturelles étant notamment des fibres de cellulose, par une composition liquide comportant un additif anti-feu selon l'invention décrite. Dans une variante, on y rattache une étape de séchage/prise de la composition liquide comportant l'additif anti-feu qui a été enduite sur le matelas. The invention also relates, in itself, to a step of coating a fiber mat, said fibers being at least for part of them natural fibers, said natural fibers being in particular cellulose fibers, for example a liquid composition comprising an anti-fire additive according to the invention described. In a variant, there is attached a drying / setting step of the liquid composition comprising the fire-resistant additive which has been coated on the mattress.
Grâce à l'invention, on simplifie la fabrication des éléments de couverture car on obtient en une seule opération la coloration avec la composition colorante comportant au moins un pigment et au moins une résine et la protection contre le feu puisque la composition comporte également du graphite et un agent de refroidissement, le tout se faisant par voie humide avec enduction au rouleau. La mise en œuvre de rouleaux permet une application contrôlée avec une certaine pression de la composition, ce qui conduit à une meilleure prise/incorporation des éléments de la composition dans le matelas de fibres, notamment des flocons ou paillettes de graphite. L'enduction au rouleau permet également d'envisager de réaliser des motifs colorés particuliers sur le matelas. Thanks to the invention, the production of the cover elements is simplified because in a single operation the coloring with the coloring composition comprising at least one pigment and at least one resin and the protection against fire is obtained since the composition also comprises graphite. and a coolant, all wet by roll coating. The implementation of rollers allows a controlled application with a certain pressure of the composition, which leads to a better grip / incorporation of the elements of the composition in the fiber mat, in particular flakes or flakes of graphite. The roll coating also makes it possible to envisage making particular colored patterns on the mattress.
La présente invention, sans qu'elle en soit pour autant limitée, va maintenant être exemplifiée avec la description qui suit de modes de réalisation et de mise en œuvre en relation avec : The present invention, without being limited thereby, will now be exemplified with the following description of embodiments and implementation in relation to:
la Figure 1 qui représente un dispositif pour enduction d'un matelas de fibres naturelles qui sont ici des fibres de cellulose. Figure 1 which shows a device for coating a mat of natural fibers which are here cellulose fibers.
Le dispositif d'enduction 1 de la Figure 1 est spécialement configuré pour la mise en œuvre du procédé de l'invention car il permet une enduction homogène d'une composition liquide 5 comportant un additif anti-feu grâce à rouleau d'enduction 2 qui trempe/baigne en partie dans ladite composition 5. La composition liquide 5 comportant l'additif anti-feu est contenue dans un réservoir 6 d'enduction du dispositif 1 et est maintenue sous agitation constante par un agitateur 7 afin que ladite composition reste sensiblement homogène. Les axes de rotation du rouleau d'enduction 2 et de l'agitateur 7 sont parallèles entre eux. Un contre-rouleau 3 presse le matelas 4 de fibres de cellulose contre le rouleau d'enduction 2. Des moyens de réglage et de régulation de la pression du contre-rouleau sont mis en œuvre. The coating device 1 of FIG. 1 is specially configured for the implementation of the method of the invention since it allows a homogeneous coating of a liquid composition comprising an anti-fire additive by means of a coating roll 2 which quenching / bath partially in said composition 5. The liquid composition 5 comprising the fire-resistant additive is contained in a coating tank 6 of the device 1 and is kept under constant stirring by an agitator 7 so that said composition remains substantially homogeneous . The axes of rotation of the coating roll 2 and the stirrer 7 are parallel to each other. A counter-roller 3 presses the mattress 4 of cellulose fibers against the coating roll 2. Counter pressure adjusting and regulating means are implemented.
Dans cet exemple, les fibres de cellulose sont sous forme d'un matelas de fibres de cellulose continu qui défile continûment entre le rouleau d'enduction 2 et le contre- rouleau 3.
La composition liquide 5 comportant l'additif anti-feu provient de préférence d'un système de stockage et/ou de préparation amont de ladite composition non représenté et le dispositif comporte des moyens de transfert et de régulation du niveau de la composition liquide 5 dans le réservoir 6 d'enduction. Parmi les moyens de réglage de la quantité de composition liquide 5 comportant l'additif anti-feu qui se dépose sur le matelas de fibres de cellulose et qui se retrouve donc dans le produit fini, on peut mentionner le réglage du niveau de la composition liquide 5 dans le réservoir 6 d'enduction faisant que le rouleau d'enduction 2 trempe plus ou moins dans la composition liquide. In this example, the cellulose fibers are in the form of a continuous cellulose fiber mat continuously passing between the coating roller 2 and the counter roller 3. The liquid composition comprising the fire-resistant additive preferably comes from a system for storing and / or preparing upstream of said composition, not shown, and the device comprises means for transferring and regulating the level of the liquid composition 5 in the coating tank 6. Among the means for adjusting the amount of liquid composition comprising the fire-resistant additive which is deposited on the cellulose fiber mat and which is therefore found in the finished product, it is possible to mention the adjustment of the level of the liquid composition. 5 in the coating tank 6 causing the coating roll 2 to quench more or less in the liquid composition.
Une circulation en boucle est avantageusement mise en œuvre entre le réservoir A loop circulation is advantageously implemented between the reservoir
6 d'enduction et le système amont de stockage et/ou de préparation. Ce système amont comporte des moyens de préparation de la composition liquide 5 comportant l'additif anti-feu avec un mélangeur permettant des mélanges à des vitesses différentes. Une pompe volumétrique à basse pression est mise en œuvre entre le système de stockage et/ou préparation et le réservoir 6 d'enduction. 6 of coating and the upstream system of storage and / or preparation. This upstream system comprises means for preparing the liquid composition comprising the fire-resistant additive with a mixer allowing mixtures at different speeds. A low pressure displacement pump is implemented between the storage system and / or preparation and the coating tank 6.
Typiquement, on prépare une composition liquide 5 de type composition colorante comportant l'additif anti-feu en mélangeant tout d'abord du pigment dans de l'eau dans un mélangeur à haute vitesse de mélange. De préférence, on ajoute des agents surfactants afin de faciliter le mélange entre l'eau et le/les pigments. Ensuite, on ajoute la colémanite toujours dans le mélangeur à haute vitesse de mélange, de préférence par ajout progressif de la colémanite. Une fois ce mélange précédent réalisé, on ajoute progressivement le graphite que l'on mélange cette fois à vitesse plus faible. Ensuite, on ajoute une ou plusieurs résines compatibles que l'on mélange à cette vitesse plus faible ou à une vitesse encore plus faible. Au cours de ces phases, on ajuste, si nécessaire, la viscosité et/ou d'autres paramètres. A cette fin, on peut jouer sur les quantités des produits mis en œuvre, notamment eau, pigment(s), résine(s) et/ou on peut ajouter d'autres produits. A noter que dans d'autres modalités de réalisation d'une composition liquide comportant l'additif anti-feu, l'ordre et/ou la manière d'incorporer au mélange les composés peuvent être différents. Typically, a liquid composition of the dye composition type comprising the fire retardant is prepared by first mixing pigment in water in a high speed mixing mixer. Surfactants are preferably added to facilitate mixing between the water and the pigment (s). Then, the colemanite is still added to the mixer at high mixing speed, preferably by gradual addition of the colemanite. Once this mixture has been achieved, the graphite is gradually added and this time is mixed at a lower speed. Then, one or more compatible resins are added which are mixed at this lower speed or at an even lower speed. During these phases, viscosity and / or other parameters are adjusted if necessary. To this end, we can play on the quantities of the products used, including water, pigment (s), resin (s) and / or we can add other products. Note that in other embodiments of a liquid composition comprising the fire additive, the order and / or the manner of incorporating into the mixture the compounds may be different.
La colémanite est un agent de refroidissement, c'est-à-dire que c'est une substance qui évite une trop forte élévation de chaleur du matelas de fibres lorsque ce dernier est chauffé. En effet, en lui-même, le graphite est conducteur de chaleur. Or, au cours de l'opération de séchage du matelas de fibres après enduction, le matelas est chauffé pour éliminer l'eau / l'humidité restant dans le matelas. En effet, la solution visqueuse contenant entre autres le graphite, est appliquée sur le matelas alors qu'il contient encore une certaine humidité. Ce chauffage pour séchage, qui permet également la prise/le séchage de la composition liquide d'enduction, va donc également chauffer le graphite et la température du graphite au contact du matelas de fibres risque d'entraîner un sur-chauffage de ces fibres et donc un risque d'endommagement des
fibres. L'agent de refroidissement a donc pour rôle de contrôler la température au niveau du matelas de fibres grâce à la libération de molécules d'eau dans le cas d'espèce de la colémanite. Colemanite is a coolant, that is, it is a substance that avoids too high a rise in heat of the fiber mat when it is heated. Indeed, in itself, graphite is heat conductor. However, during the drying operation of the fiber mat after coating, the mattress is heated to remove water / moisture remaining in the mattress. Indeed, the viscous solution containing among others graphite, is applied on the mattress while it still contains a certain humidity. This heating for drying, which also allows the setting / drying of the liquid coating composition, will therefore also heat the graphite and the temperature of the graphite in contact with the fiber mat may cause overheating of these fibers and therefore a risk of damage to fibers. The cooling agent therefore has the role of controlling the temperature at the level of the fiber mat with the release of water molecules in the case of the species of colemanite.
On comprend donc qu'un agent de refroidissement, dans le cadre de l'invention, peut correspondre à une substance qui, par une réaction physicochimique, provoque un abaissement de température, vaporisation de l'eau dans le cas de la colémanite, et/ou par un effet physique limite la transmission de chaleur par effet barrière et/ou de réflexion. It is therefore understood that a cooling agent, in the context of the invention, may correspond to a substance which, by a physicochemical reaction, causes a lowering of temperature, vaporization of water in the case of colemanite, and or by a physical effect limits the heat transfer by barrier and / or reflection.
La composition liquide comportant l'additif anti-feu qui est enduite sur le matelas est de préférence sous forme liquide d'une fluidité déterminée pour permettre à une partie de ladite composition liquide comportant l'additif anti-feu de pouvoir diffuser au moins en partie à l'intérieur de l'épaisseur du matelas de fibres de cellulose. Ainsi, la composition liquide comportant l'additif anti-feu imprègne, au moins en partie, l'épaisseur du matelas en plus de couvrir en surface au moins une des deux faces du matelas de fibres de cellulose. De préférence, une seule des deux faces du matelas de fibres de cellulose est enduite par la composition liquide comportant l'additif anti-feu. Dans une variante de mise en œuvre, la composition liquide comportant l'additif anti-feu peut être d'une consistance plus pâteuse avec application au couteau ou racloir sur le matelas de fibres de cellulose. The liquid composition comprising the fire-resistant additive which is coated on the mattress is preferably in liquid form with a specific fluidity to allow a part of said liquid composition comprising the fire-resistant additive to be able to diffuse at least in part inside the thickness of the cellulose fiber mat. Thus, the liquid composition comprising the fire-resistant additive impregnates, at least in part, the thickness of the mattress in addition to covering on the surface at least one of the two faces of the cellulose fiber mat. Preferably, only one of the two faces of the cellulose fiber mat is coated with the liquid composition comprising the fire retardant additive. In an alternative embodiment, the liquid composition comprising the fire-resistant additive may be of a more pasty consistency with application to the knife or scraper on the cellulose fiber mat.
Le graphite mis en œuvre a des gammes de tailles et formes de particules déterminées et, de préférence, on met en œuvre du graphite sous forme de flocons ou paillettes qui restent essentiellement en surface du matelas de fibres de cellulose et qui diffusent peu dans son épaisseur. The graphite employed has a range of sizes and shapes of determined particles and, preferably, it uses graphite in the form of flakes or flakes which remain essentially on the surface of the cellulose fiber mat and which diffuse little in its thickness. .
En particulier, le graphite est choisi, notamment en forme/structure et/ou taille, ainsi que les paramètres opérationnels du procédé de réalisation des éléments de couverture, pour qu'il reste en suspension dans la composition liquide jusqu'au moment de son application et qu'il reste inerte au cours du séchage ultérieur à l'enduction et de l'imprégnation par le bitume. Il est en effet préférable qu'il n'y ait pas d'expansion du graphite avant la fin du procédé de réalisation des éléments de couverture. In particular, the graphite is chosen, in particular in shape / structure and / or size, as well as the operational parameters of the process for producing the covering elements, so that it remains in suspension in the liquid composition until it is applied. and that it remains inert during post-coating drying and bitumen impregnation. It is indeed preferable that there is no expansion of the graphite before the end of the process of producing the covering elements.
Par rapport à des procédés de dépôt en phase sèche de graphite, le procédé de la présente invention peut permettre une diffusion plus ou moins importante du graphite dans l'épaisseur du matelas de fibres de cellulose si on le souhaite en modifiant la taille et/ou la forme du graphite utilisé. With respect to graphite dry phase deposition processes, the process of the present invention can allow more or less diffusion of the graphite into the thickness of the cellulose fiber mat if desired by changing the size and / or the shape of the graphite used.
Après enduction du matelas de fibres de cellulose par la composition liquide comportant l'additif anti-feu, le matelas est séché dans un four de séchage ce qui permet à la fois la prise/réticulation de la composition liquide comportant l'additif anti-feu et une élimination de l'eau/humidité pouvant encore être contenu dans le matelas. Le four de séchage est à une température comprise entre 150°C et 400 °C et, de préférence, comprise entre 200 °C et 300 ° C. En effe,t pour imprégnation par le bitume à
chaud des fibres de cellulose, de préférence alors en plaques et non plus sous forme d'un matelas continu, il est souhaitable que le matelas ou les plaques soient essentiellement sèches. After coating the cellulose fiber mat with the liquid composition comprising the fire-resistant additive, the mattress is dried in a drying oven which allows both the setting / crosslinking of the liquid composition comprising the fire-resistant additive and removal of water / moisture that can still be contained in the mattress. The drying oven is at a temperature between 150 ° C and 400 ° C and preferably between 200 ° C and 300 ° C. In fact, for impregnation with bitumen to When the cellulose fibers are hot, preferably in sheets and no longer in the form of a continuous mattress, it is desirable for the mat or the plates to be substantially dry.
En général, après enduction par la composition liquide comportant l'additif anti- feu, le matelas de fibres de cellulose est conformé au cours d'une étape de conformation du matelas pour, par exemple, réalisation d'ondulations, puis est ensuite passé dans le four de séchage. On peut cependant prévoir un moyen spécifique de séchage/prise de la composition liquide comportant l'additif anti-feu, différent du four de séchage, entre l'enduction et la conformation. Après séchage dans le four de séchage, le matelas de fibres de cellulose est découpé en plaques et ce sont ces plaques qui sont ensuite imprégnées de bitume à chaud. Jusqu'au découpage du matelas en plaques, le processus est continu, le matelas de fibres de cellulose défilant en continu pour enduction, conformation et séchage dans le four de séchage.
In general, after coating with the liquid composition comprising the fire-resistant additive, the cellulose fiber mat is shaped during a conformation step of the mattress for, for example, producing corrugations, and is then passed through the drying oven. However, it is possible to provide a specific means of drying / setting the liquid composition comprising the fire-resistant additive, different from the drying oven, between the coating and the conformation. After drying in the drying oven, the cellulose fiber mat is cut into plates and it is these plates which are then impregnated with hot bitumen. Until the cutting of the mattress plate, the process is continuous, the cellulose fiber mat continuously scrolling for coating, shaping and drying in the drying oven.
Claims
1 . Procédé de réalisation d'un élément de couverture en fibres imprégné de bitume comportant une étape d'enduction d'au moins une de deux faces d'un matelas (4) de fibres, lesdites fibres étant au moins pour une partie d'entre elles des fibres naturelles, lesdites fibres naturelles étant notamment des fibres de cellulose, suivie d'une étape d'imprégnation par le bitume, l'enduction étant réalisée par une composition liquide (5) comportant au moins une résine et/ou au moins un pigment, caractérisé en ce que la composition liquide est une composition colorante comportant au moins un pigment et au moins une résine et en ce qu'on ajoute à la composition liquide (5) un additif ayant des propriétés anti-feu et comportant au moins du graphite et un agent de refroidissement. 1. Method for producing a fiber covering element impregnated with bitumen comprising a step of coating at least one of two faces of a mat (4) of fibers, said fibers being at least for part of them natural fibers, said natural fibers being in particular cellulose fibers, followed by a step of impregnation with bitumen, the coating being carried out by a liquid composition (5) comprising at least one resin and/or at least one pigment , characterized in that the liquid composition is a coloring composition comprising at least one pigment and at least one resin and in that an additive having anti-fire properties and comprising at least graphite is added to the liquid composition (5). and a cooling agent.
2. Procédé selon la revendication 1 , dans lequel l'agent de refroidissement de l'additif anti-feu est de la colémanite. 2. Method according to claim 1, wherein the cooling agent of the anti-fire additive is colemanite.
3. Procédé selon l'une des revendications 1 et 2, dans lequel le graphite est en flocons ou en paillettes. 3. Method according to one of claims 1 and 2, in which the graphite is in flakes or flakes.
4. Procédé selon l'une quelconque des revendications précédentes, dans lequel: 4. Method according to any one of the preceding claims, in which:
- la au moins une résine est choisie parmi : les résines époxydes, les résines polyuréthanes, les résines polyurées, les résines polyurée-formaldéhydes, les résines mélamines-formaldéhydes, les résines époxyvinylesters ou les résines vinylesters, et- the at least one resin is chosen from: epoxy resins, polyurethane resins, polyurea resins, polyurea-formaldehyde resins, melamine-formaldehyde resins, epoxyvinylester resins or vinyl ester resins, and
- le au moins un pigment est choisi parmi : les oxydes métalliques tels que l'oxyde de fer et l'oxyde de chrome. - at least one pigment is chosen from: metal oxides such as iron oxide and chromium oxide.
5 Procédé selon l'une quelconque des revendications précédentes, dans lequel la quantité de résine représente de 0,5 à 3 % en poids de l'élément de couverture, la quantité de pigment représente de 0,5 à 3 % en poids de l'élément de couverture, la quantité d'agent de refroidissement représente de 1 à 7 % en poids de l'élément de couverture, et la quantité de graphite représente de 1 à 7 % en poids de l'élément de couverture. 5 Method according to any one of the preceding claims, in which the quantity of resin represents 0.5 to 3% by weight of the covering element, the quantity of pigment represents 0.5 to 3% by weight of the covering element, the amount of cooling agent represents 1 to 7% by weight of the covering element, and the amount of graphite represents 1 to 7% by weight of the covering element.
6. Procédé selon l'une quelconque des revendications précédentes, comportant en outre une étape de séchage et de prise de la composition liquide comportant l'additif anti-feu qui a été enduite sur le matelas. 6. Method according to any one of the preceding claims, further comprising a step of drying and setting the liquid composition comprising the anti-fire additive which has been coated on the mattress.
7. Procédé selon l'une quelconque des revendications précédentes, dans lequel le matelas de fibres est continu, ledit matelas étant découpé en plaques dans une étape de segmentation postérieure à l'étape d'enduction et antérieure à l'étape d'imprégnation par le bitume, l'imprégnation par le bitume s'effectuant sur des plaques individuelles. 7. Method according to any one of the preceding claims, in which the fiber mat is continuous, said mat being cut into plates in a segmentation step subsequent to the coating step and prior to the impregnation step by bitumen, the impregnation with bitumen taking place on individual plates.
8. Procédé selon l'une quelconque des revendications précédentes, comportant en outre une étape de conformation du matelas postérieurement à l'étape d'enduction et antérieurement à l'étape d'imprégnation par le bitume.
8. Method according to any one of the preceding claims, further comprising a step of shaping the mattress after the coating step and before the bitumen impregnation step.
9. Procédé selon l'une quelconque des revendications précédentes, dans lequel la composition liquide comportant l'additif anti-feu destinée à être enduite sur le matelas est maintenue sous agitation constante par un agitateur. 9. Method according to any one of the preceding claims, in which the liquid composition comprising the anti-fire additive intended to be coated on the mattress is kept under constant agitation by an agitator.
10. Procédé selon la revendication 9, dans lequel l'enduction du matelas (4) avec la composition liquide comportant l'additif anti-feu est réalisée au rouleau. 10. Method according to claim 9, in which the coating of the mattress (4) with the liquid composition comprising the anti-fire additive is carried out with a roller.
1 1 . Procédé selon la revendication 10, caractérisé en ce qu'on met en œuvre au moins un rouleau d'enduction (2) et un réservoir (6) d'enduction pour la composition liquide (5) comportant l'additif anti-feu, ledit au moins un rouleau d'enduction baignant au sein du réservoir (6) d'enduction dans ladite composition liquide comportant l'additif anti-feu et en ce que ledit réservoir (6) d'enduction comporte ledit agitateur (7) destiné à maintenir sous une agitation constante ladite composition (5) comportant l'additif anti- feu. 1 1 . Method according to claim 10, characterized in that at least one coating roller (2) and a coating tank (6) are used for the liquid composition (5) comprising the anti-fire additive, said at least one coating roller bathing within the coating tank (6) in said liquid composition comprising the anti-fire additive and in that said coating tank (6) comprises said agitator (7) intended to maintain under constant stirring, said composition (5) comprising the fire-fighting additive.
12. Composition liquide (5) comportant un additif anti-feu pour mise en œuvre dans le procédé de l'une quelconque des revendications 1 à 1 1 , caractérisée en ce qu'elle comporte, pour la partie de composition liquide au moins une résine et un ou des pigments, et pour la partie additif anti-feu, du graphite et un agent de refroidissement. 12. Liquid composition (5) comprising an anti-fire additive for use in the process of any one of claims 1 to 1 1, characterized in that it comprises, for the liquid composition part at least one resin and one or more pigments, and for the anti-fire additive part, graphite and a cooling agent.
13. Composition liquide (5) comportant un additif anti-feu selon la revendication 12, caractérisée en ce que l'agent de refroidissement est de la colémanite.
13. Liquid composition (5) comprising an anti-fire additive according to claim 12, characterized in that the cooling agent is colemanite.
Priority Applications (12)
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| MX2016009105A MX2016009105A (en) | 2014-01-28 | 2015-01-22 | Method for producing a covering element made from fibres impregnated with bitumen having improved fire properties, and composition. |
| KR1020167020657A KR102335757B1 (en) | 2014-01-28 | 2015-01-22 | Method for producing a covering element made from fibres impregnated with bitumen having improved fire properties, and composition |
| RU2016131321A RU2676628C2 (en) | 2014-01-28 | 2015-01-22 | Method for producing covering element made from fibers impregnated with bitumen having improved fire properties and composition |
| CA2937307A CA2937307A1 (en) | 2014-01-28 | 2015-01-22 | Method for producing a covering element made from fibres impregnated with bitumen having improved fire properties, and composition |
| JP2016547858A JP6626827B2 (en) | 2014-01-28 | 2015-01-22 | Methods and compositions for producing coated elements made from bitumen impregnated fibers having improved flame properties |
| ES15704064T ES2759550T3 (en) | 2014-01-28 | 2015-01-22 | Procedure for making a coating element in fibers impregnated with bitumen with improved fire performance |
| CN201580006091.2A CN106029977A (en) | 2014-01-28 | 2015-01-22 | Method for producing a covering element made from fibres impregnated with bitumen having improved fire properties, and composition |
| EP15704064.3A EP3099853B1 (en) | 2014-01-28 | 2015-01-22 | Method for producing a covering element made from fibres impregnated with bitumen having improved fire properties |
| US15/115,072 US10487509B2 (en) | 2014-01-28 | 2015-01-22 | Method for producing a covering element made from fibers impregnated with bitumen having improved fire properties, and composition |
| UAA201608258A UA119974C2 (en) | 2014-01-28 | 2015-01-22 | Method for producing a covering element made from fibres impregnated with bitumen having improved fire properties, and composition |
| PL15704064T PL3099853T3 (en) | 2014-01-28 | 2015-01-22 | Method for producing a covering element made from fibres impregnated with bitumen having improved fire properties |
| PH12016501397A PH12016501397A1 (en) | 2014-01-28 | 2016-07-14 | Method for producing a covering element made from fibres impregnated with bitumen having improved fire properties, and composition |
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| FR1400213A FR3016903B1 (en) | 2014-01-28 | 2014-01-28 | METHOD OF MAKING IMPROVED BITUMEN IMPREGNATED FIBER COVERING ELEMENT WITH IMPROVED FIRE BEHAVIOR, DEVICE AND COMPOSITION THEREFOR. |
| FR1400213 | 2014-01-28 |
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| WO2015114239A1 true WO2015114239A1 (en) | 2015-08-06 |
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| RU205493U1 (en) * | 2020-08-07 | 2021-07-16 | Пётр Александрович Липка | ROLLED WATERPROOFING MATERIAL |
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| EP2634306A1 (en) | 2012-02-28 | 2013-09-04 | S.A. Imperbel N.V. | Protective membrane and method for manufacturing same. |
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| DE29709804U1 (en) | 1997-05-30 | 1997-08-14 | Hoechst Trevira Gmbh & Co Kg | Flame retardant shingle |
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- 2014-01-28 FR FR1400213A patent/FR3016903B1/en not_active Expired - Fee Related
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- 2015-01-22 ES ES15704064T patent/ES2759550T3/en active Active
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- 2015-01-22 CA CA2937307A patent/CA2937307A1/en not_active Abandoned
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- 2015-01-26 AR ARP150100209A patent/AR099182A1/en unknown
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| EP2617894A1 (en) | 2012-01-20 | 2013-07-24 | Onduline | Fire-resistant bituminous cellulose cover plate and manufacturing method |
| EP2634306A1 (en) | 2012-02-28 | 2013-09-04 | S.A. Imperbel N.V. | Protective membrane and method for manufacturing same. |
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| AR099182A1 (en) | 2016-07-06 |
| JP2017508895A (en) | 2017-03-30 |
| KR20160110408A (en) | 2016-09-21 |
| PH12016501397A1 (en) | 2016-08-22 |
| RU2676628C2 (en) | 2019-01-09 |
| UA119974C2 (en) | 2019-09-10 |
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